1. Field of the Invention
Polymers with high levels of fluorine have novel properties including chemical and thermal resistance.
This invention provides a novel route to fluorinated polyethers by reacting perfluoroolefins with bis(silyl) ethers in the presence of a catalyst to produce partially fluorinated and perfluorinated copolymers and macrocyclic compounds, partially fluorinated bis(vinyl) ethers and perfluorinated bis(alkyl) ethers. The compositions of this invention are useful in vapor phase soldering, as lubricants and as heat stable oils and greases.
2. Technical Background
Hans R. Kricheldorf and Gerhard Bier, Journal of Polymer Science, Polymer Chemistry Edition, Vol. 21, 2283-2289 (1983) disclose the condensation polymerizations of bis(4-fluorophenyl) sulfone with the bis trimethylsilyl derivatives of bisphenol-A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl sulfone, 1,5-dihydroxynaphthalene, 3-hydroxybenzoic acid, and 4-hydroxybenzoic acid. These polycondensations were only successful when potassium or cesium fluoride was used as a catalyst.
Hans R. Kricheldorf and Gerhard Bier, Polymer, Vol. 25, 1151 (1984) disclose the bulk condensations of 4,4'-difluorobenzophenone and various silylated bisphenols at 220.degree. C.-320.degree. C. with cesium fluoride as a catalyst.
U.S. Pat. No. 4,474,932 discloses and claims a process for the preparation of aromatic ethers or polyethers by reacting aromatic fluorine compounds, in which one or more fluorine substituents are attached to an aromatic nucleus, with trialkylsilyl derivatives of phenols, in which one or more trialkylsilyl groups are attached to the residue of a mono or polyphenol, or by reacting trialkylsilyl derivatives of fluorophenols with elimination of trialkylfluorosilane.
D. G. Saunders, Synthesis, No. 5, Communications, 377 (1988) discloses the reaction of aryl silyl ethers with alkyl halide, or activated aryl halide, and tetrabutylammonium fluoride, to give alkyl aryl ethers or diaryl ethers, respectively. Alkyl silyl ethers under the same or related reaction conditions give mainly the corresponding alcohol, and only very low yields of the ether.
U.S. Pat. No. 3,549,606 claims fluoroalkyl ether polymers of alicyclic fluoroolefins comprised of repeating units of the structure: ##STR1## wherein n=1-7, y is at least 2 and m is a number from 1-12.
U.S. Pat. No. 3,497,563 claims ethers of the formula: ##STR2## wherein: 5 E is selected from the group consisting of hydrogen, fluorine and --CH.sub.2 OH and may be --CH.sub.2 OH only when T, G and Z are halogen;
G is selected from the group consisting of fluorine and --OCH.sub.2 (CF.sub.2).sub.m D and is fluorine when T is --CH.sub.2 (CF.sub.2).sub.n D; PA1 T is selected from the group consisting of bromine, chlorine and --OCH.sub.2 (CF.sub.2).sub.m D and is a halogen when G and Z are --OCH.sub.2 (CF.sub.2).sub.m D; PA1 Z is selected from the group consisting of fluorine and --OCH.sub.2 (CF.sub.2).sub.m D and is fluorine when T is --OCH.sub.2 (CF.sub.2).sub.m D; PA1 D is selected from the group consisting of hydrogen and fluorine; and PA1 n is a number from 1-7 and each m expression is a number from 1 to 12. That invention also claims a method for producing an unsaturated fluorine containing alicyclic ether by reacting cyclic olefin of the formula: ##STR3## where L is selected from the group consisting of fluorine, bromine and chlorine with a fluoroalkanol, in the presence of an alkali metal hydroxide. PA1 R is a diradical of the formula --C.sub.x H.sub.2x-y F.sub.y --, where x is an integer from 2 to 20, y is 0 or an integer from 1 to 2x for a given value of x, but with the additional proviso that the carbon atoms containing the free valence of the diradical not be attached to fluorine atoms, and when x is a integer from 4 to 20 some of the carbon atoms may be internally interrupted with oxygen atoms forming ether structures and with the proviso that the oxygen atoms be separated by two or more carbon atoms; --C.sub.6 H.sub.4-a F.sub.a --, wherein a is 0, 1, 2, 3, or 4; --C.sub.10 H.sub.6-b F.sub.b --, wherein b is 0 or an integer from 1 to 6, with the proviso that the radical bonds are not on adjacent carbon atoms; --C.sub.12 H.sub.8-c F.sub.c --, wherein c is 0 or an integer from 1 to 8, with the proviso that the radical bonds are not on adjacent carbon atoms; and --CH.sub.4-d F.sub.d --R.sup.1 --C.sub.6 H.sub.4-e F.sub.e --, wherein d and e are independently 0 or an integer from 1 to 4, R.sup.1 is --C.sub.x H.sub.2x-f F.sub.f --, wherein f is 0 or an integer from 1 to 2x; PA1 (D) R.sub.f.sup.1 (F)C.dbd.C(R.sub.f.sup.2)OROC(R.sub.f.sup.2).dbd.C(F)R.sub.f.sup.1, PA1 (E) R.sub.f.sup.1 (F)C.dbd.C(F)OR.sup.8 OC(F).dbd.C(F)R.sub.f.sup.1, and PA1 (E') R.sub.f.sup.1 R.sub.f.sup.2 C.dbd.C(R.sub.f.sup.6)OR.sup.8 OC(R.sub.f.sup.6).dbd.CR.sub.f.sup.2 R.sub.f.sup.1 PA1 (M) R.sub.f.sup.4 CF.sub.2 CF(R.sub.f.sup.5)OR.sub.f.sup.3 OCF(R.sub.f.sup.5)CF.sub.2 R.sub.f.sup.4, PA1 (N) R.sub.f.sup.4 CF.sub.2 CF.sub.2 OR.sub.f.sup.3 OCF.sub.2 CF.sub.2 R.sub.f.sup.4, and PA1 (N') R.sub.f.sup.4 R.sub.f.sup.5 CFCF(R.sub.f.sup.6)OR.sub.f.sup.3 OCF(R.sub.f.sup.6)CFR.sub.f.sup.4 R.sub.f.sup.5